Double metal cyanide-catalyzed, low unsaturation polyethers from boron-containing starters

Abstract

The present invention provides a process for the double metal cyanide (DMC)-catalyzed production of low unsaturation polyethers from boron-containing starters. The polyethers produced by the inventive process may be reacted with one or more isocyanates to provide polyurethane products including coatings, adhesives, sealants, elastomers, foams and the like. The inventive process may be used to prepare fuel additives from C 9 -C 30 boron-containing polyethers, more particularly from C 13 alcohols.

1. A process for the production of a polyether polyol comprising: adding to a boron-containing starter compound from about 0.75 equivalents to about 7 equivalents of an acid per equivalent of boron; and 
       polyoxyalkylating the boron-containing starter compound with an alkylene oxide in the presence of a double metal cyanide (DMC) catalyst, wherein the boron-containing starter compound is a C 4 -C 40  alcohol. 
     
     
       2. The process according to  claim 1 , wherein the boron-containing starter compound is a C 9 -C 30  alcohol. 
     
     
       3. The process according to  claim 1 , wherein the boron-containing starter compound is a C 13  alcohol. 
     
     
       4. The process according to  claim 1 , wherein the boron-containing starter compound comprises from about 0.01 to about 20 meq/kg of boron compounds. 
     
     
       5. The process according to  claim 1 , wherein the boron-containing starter compound comprises from about 0.4 to about 10 meq/kg of boron compounds. 
     
     
       6. The process according to  claim 1 , wherein the boron-containing starter compound comprises from about 1 to about 8 meq/kg of boron compounds. 
     
     
       7. The process according to  claim 1 , wherein about 0.8 equivalents to about 5 equivalents of acid is added per equivalent of boron. 
     
     
       8. The process according to  claim 1 , wherein about 0.95 equivalents to about 4 equivalents of acid is added per equivalent of boron. 
     
     
       9. The process according to  claim 1 , wherein the acid is chosen from mineral acids, organic carboxylic acids, phosphonic acids, sulfonic acids and combinations thereof. 
     
     
       10. The process according to  claim 1 , wherein the acid is chosen from citric acid, 1,3,5-benzene tricarboxylic acids, phosphonic acids, p-toluenesulfonic acid, hydrochloric acid, hydrobromic acid, sulfuric acid, formic acid, oxalic acid, acetic acid, maleic acid, maleic anhydride, succinic acid, succinic anhydride, adipic acid, adipoyl chloride, adipic anhydride, thionyl chloride, phosphorous trichloride, carbonyl chloride, sulfur trioxide, thionyl chloride phosphorus pentoxide, phosphorous oxytrichloride and combinations thereof. 
     
     
       11. The process according to  claim 1 , wherein the acid is phosphoric acid. 
     
     
       12. The process according to  claim 1 , wherein from about 1 to about 7 equivalents of phosphoric acid are added per equivalent of boron. 
     
     
       13. The process according to  claim 1 , wherein from about 2 to about 5 equivalents of phosphoric acid are added per equivalent of boron. 
     
     
       14. The process according to  claim 1 , wherein from about 2.5 to about 4.5 equivalents of phosphoric acid are added per equivalent of boron. 
     
     
       15. The process according to  claim 1 , wherein the alkylene oxide is chosen from ethylene oxide, propylene oxide, 1,2- and 2,3-butylene oxide, isobutylene oxide, epichlorohydrin, cyclohexene oxide, styrene oxide and C 5 -C 30  α-alkylene oxides. 
     
     
       16. The process according to  claim 1 , wherein the alkylene oxide is chosen from propylene oxide, 1,2- and 2,3-butylene oxide and isobutylene oxide. 
     
     
       17. The process according to  claim 1 , wherein the DMC catalyst is a zinc hexacyanocobaltate. 
     
     
       18. The process according to  claim 1 , wherein the unsaturation of the polyether is less than about 0.05 meq/g. 
     
     
       19. The process according to  claim 1 , wherein the unsaturation of the polyether is less than about 0.04 meq/g. 
     
     
       20. In a process of producing one of a polyurethane coating, adhesive, sealant, elastomer and foam, the improvement comprising including the polyether polyol by the process according to  claim 1 . 
     
     
       21. A process comprising: 
       producing a fuel additive by adding to a boron-containing starter compound from about 0.75 equivalents to about 7 equivalents of an acid per equivalent of boron; 
       and polyoxyalkylating the boron-containing starter compound with an alkylene oxide in the presence of a double metal cyanide (DMC) catalyst, wherein the boron-containing starter compound is a C 9 -C 30  alcohol. 
     
     
       22. The process according to  claim 21 , wherein the boron-containing starter compound is a C 13  alcohol. 
     
     
       23. The process according to  claim 21 , wherein the boron-containing starter compound comprises from about 0.01 to about 20 meq/kg of boron compounds. 
     
     
       24. The process according to  claim 21 , wherein the boron-containing starter compound comprises from about 0.4 to about 10 meq/kg of boron compounds. 
     
     
       25. The process according to  claim 21 , wherein the boron-containing starter compound comprises from about 1 to about 8 meq/kg of boron compounds. 
     
     
       26. The process according to  claim 21 , wherein about 0.8 equivalents to about 5 equivalents of acid is added per equivalent of boron. 
     
     
       27. The process according to  claim 21 , wherein about 0.95 equivalents to about 4 equivalents of acid is added per equivalent of boron. 
     
     
       28. The process according to  claim 21 , wherein the acid is chosen from mineral acids, organic carboxylic acids, phosphonic acids, sulfonic acids and combinations thereof. 
     
     
       29. The process according to  claim 21 , wherein the acid is chosen from citric acid, 1,3,5-benzene tricarboxylic acids, phosphonic acids, p-toluenesulfonic acid, hydrochloric acid, hydrobromic acid, sulfuric acid, formic acid, oxalic acid, acetic acid, maleic acid, maleic anhydride, succinic acid, succinic anhydride, adipic acid, adipoyl chloride, adipic anhydride, thionyl chloride, phosphorous trichloride, carbonyl chloride, sulfur trioxide, thionyl chloride phosphorus pentoxide, phosphorous oxytrichloride and combinations thereof. 
     
     
       30. The process according to  claim 21 , wherein the acid is phosphoric acid. 
     
     
       31. The process according to  claim 21 , wherein from about 1 to about 7 equivalents of phosphoric acid are added per equivalent of boron. 
     
     
       32. The process according to  claim 21 , wherein from about 2 to about 5 equivalents of phosphoric acid are added per equivalent of boron. 
     
     
       33. The process according to  claim 21 , wherein from about 2.5 to about 4.5 equivalents of phosphoric acid are added per equivalent of boron. 
     
     
       34. The process according to  claim 21 , wherein the alkylene oxide is chosen from ethylene oxide, propylene oxide, 1,2- and 2,3-butylene oxide, isobutylene oxide, epichlorohydrin, cyclohexene oxide, styrene oxide and C 5 -C 30  α-alkylene oxides. 
     
     
       35. The process according to  claim 21 , wherein the alkylene oxide is chosen from propylene oxide, 1,2- and 2,3-butylene oxide and isobutylene oxide. 
     
     
       36. The process according to  claim 21 , wherein the DMC catalyst is a zinc hexacyanocobaltate. 
     
     
       37. The process according to  claim 21 , wherein the unsaturation of the fuel additive is less than about 0.05 meq/g. 
     
     
       38. The process according to  claim 21 , wherein the unsaturation of the fuel additive is less than about 0.04 meq/g.